Breathable hydrostatically-resistant structures

ABSTRACT

The invention provides a breathable structure that includes a fibrous substrate and a cross-linked polymer that contains hydrophobic moieties. The fibrous substrate contains a plurality of fibers, and the cross-linked polymer coats portions of the plurality of fibers.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application Ser.No. 62/700,020, filed on Jul. 18, 2018, the entire contents of which arehereby incorporated herein by reference.

FIELD OF THE INVENTION

The present disclosure generally relates to breathable structures (e.g.textile materials) having desirable hydrostatic resistance.

BACKGROUND OF THE INVENTION

Outdoor enthusiasts and others have long demanded functional articles,such as water-resistant outerwear, to protect them from the elements.Typically, this demand has been met by structures such as fabric orinsulation having water-proof or water-repellent films or membraneslaminated thereto. Such films/membranes impart improved hydrostaticresistance to structures, making them effective at preventing orreducing the ability of water to penetrate through the structure to thewearer. However, to maintain comfort, in addition to inhibiting waterreaching the body from outside clothing, a water-repellent orwater-proof article should also be able to remove vapor produced by thebody (e.g., during physical exertion). Unfortunately, although sucharticles are often classified as being breathable, they in fact do notoffer significant moisture vapor transport. Exceptions include certainmonolithic membrane films, which are used as breathable barriers intextile structures such as outerwear. Such monolithic membranes promotethe permeation of water vapor from within a structure through the use ofa hydrophilic polymer layer which absorbs the water vapor and transmitsit to the external environment. However, monolithic membranes typicallyexperience significant swelling of the hydrophilic layer, whichsignificantly alters the vapor removal characteristics of the membraneand user comfort.

Thus, generally speaking, there is an inverse relationship between thelevel of an article's hydrostatic resistance and its ability and topermit the escape of vapor from within. Consequently, the tradeoff forwater-resistant articles is compromised performance characteristics,such as comfort and breathability. Further, many breathable articlestend to have very limited insulating properties. Still further, fibroussubstrates (e.g., fabrics) laminated to certain membrane types tend tobe inflexible and/or generate noise when in use. Accordingly, despiteclaims, many waterproof and water-repellant articles tend to suffer fromless-than desirable attributes, including limited insulative properties,and undesirable moisture vapor transmission rates and air permeability.

Thus, a need remains for breathable structures useful, e.g., inouterwear articles, that offer desirable hydrostatic resistance withoutunduly compromising other properties, such as moisture vaportransmission rates and air permeability.

While certain aspects of conventional technologies have been discussedto facilitate disclosure of the disclosure, Applicant in no waydisclaims these technical aspects, and it is contemplated that theclaimed disclosure may encompass one or more of the conventionaltechnical aspects discussed herein.

In this specification, where a document, act or item of knowledge isreferred to or discussed, this reference or discussion is not anadmission that the document, act or item of knowledge or any combinationthereof was, at the priority date, publicly available, known to thepublic, part of common general knowledge, or otherwise constitutes priorart under the applicable statutory provisions; or is known to berelevant to an attempt to solve any problem with which thisspecification is concerned.

SUMMARY OF THE INVENTION

Briefly, the present invention satisfies the need for breathablestructures that offer desirable hydrostatic resistance without undulycompromising other properties, such as moisture vapor transmission ratesand air permeability. The present disclosure may address one or more ofthe problems and deficiencies of the art discussed above. However, it iscontemplated that the invention may prove useful in addressing otherproblems and deficiencies in a number of technical areas. Therefore, theclaimed invention should not necessarily be construed as limited toaddressing any of the particular problems or deficiencies discussedherein.

Certain embodiments of the presently-disclosed breathable structures,articles comprising the breathable structures, and methods for makingthe breathable structures have several features, no single one of whichis solely responsible for their desirable attributes. Without limitingthe scope of the structures, articles, and methods as defined by theclaims that follow, their more prominent features will now be discussedbriefly. After considering this discussion, and particularly afterreading the section of this specification entitled “Detailed Descriptionof the Invention,” one will understand how the features of the variousembodiments disclosed herein provide a number of advantages over thecurrent state of the art. For example, embodiments of the inventivebreathable structure offer desirable hydrostatic resistance whilemaintaining a desirable moisture vapor transmission rate and/or airpermeability.

In a first aspect, the invention provides a breathable structurecomprising a fibrous substrate and a cross-linked polymer comprisinghydrophobic moieties, wherein the fibrous substrate comprises aplurality of fibers, and wherein the cross-linked polymer coats portionsof the plurality of fibers.

In a second aspect, the invention provides an article comprising thebreathable structure according to the first aspect of the invention.

In a third aspect, the invention provides a method of making thebreathable structure according to the first aspect of the invention, orthe article according to the second aspect of the invention.

These and other features and advantages of this invention will becomeapparent from the following detailed description of the various aspectsof the invention taken in conjunction with the appended claims and theaccompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

The subject matter which is regarded as the invention is particularlypointed out and distinctly claimed in the claims at the conclusion ofthe specification. The foregoing and other features, aspects, andadvantages of the disclosure will be readily understood from thefollowing detailed description taken in conjunction with theaccompanying drawings, which are not necessarily drawn to scale, whereinlike numerals denote like elements, and wherein:

FIG. 1 depicts a portion of a nonwoven web comprising polyester fibers.

FIG. 2 is an enlarged view of fibers in an embodiment of nonwoven web.

DETAILED DESCRIPTION OF THE INVENTION

Aspects of the present invention and certain features, advantages, anddetails thereof, are explained more fully below. Descriptions ofwell-known materials, fabrication tools, processing techniques, etc.,are omitted so as to not unnecessarily obscure the disclosure in detail.It should be understood, however, that the detailed description and anyspecific example(s), while indicating embodiments of the invention, aregiven by way of illustration only, and are not by way of limitation.Various substitutions, modifications, additions and/or arrangementswithin the spirit and/or scope of the underlying inventive concepts willbe apparent to those skilled in the art from this disclosure.

Embodiments of the present invention provide structures havinghydrostatic resistance akin to that afforded by a membrane, but withoutthe accompanying loss of breathability or air permeability.

In a first aspect, the invention provides a breathable structurecomprising a fibrous substrate and a cross-linked polymer comprisinghydrophobic moieties, wherein the fibrous substrate comprises aplurality of fibers, and wherein the cross-linked polymer coats portionsof the plurality of fibers.

As used herein, the fibrous substrate is a substrate that comprises aplurality of fibers. For example, in some embodiments, the fibroussubstrate is fabric, flannel, denim, a nonwoven, a woven, or a knitstructure.

In some embodiments, the fibrous substrate is or comprises one or morenonwovens, for example, spunbonded webs (e.g., comprising filaments),melt blown webs, multi-directional, single- or multi-layer carded webs,air-laid webs, wet-laid webs, spunlaced webs, high-loft nonwoveninsulation, low-loft non-woven insulation, needled nonwoven (e.g., highdensity needled non-woven), fleece, and/or composite webs comprisingmore than one nonwoven layer.

In some embodiments, the fibrous substrate is or comprises one or morewovens, for example: woven structures, twill woven structures, satinwoven structures (the foregoing optionally being reinforced structures,e.g., with double or multiple warps and/or wefts); knits, felts, fleecesand/or needle-punched structures.

In some embodiments, the fibrous substrate is flannel. In someembodiments, the fibrous substrate is denim.

In some embodiments, the breathable structure and/or the fibroussubstrate has a thickness of 0.9 to 50 mm (e.g., 0.9, 1.0, 1.1, 1.2,1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6,2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0,4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4,5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8,6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2,8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6,9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8,10.9, 11.0, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0,12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2,13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, 14.0, 14.1, 14.2, 14.3, 14.4,14.5, 14.6, 14.7, 14.8, 14.9, 15.0, 15.1, 15.2, 15.3, 15.4, 15.5, 15.6,15.7, 15.8, 15.9, 16.0, 16.1, 16.2, 16.3, 16.4, 16.5, 16.6, 16.7, 16.8,16.9, 17.0, 17.1, 17.2, 17.3, 17.4, 17.5, 17.6, 17.7, 17.8, 17.9, 18.0,18.1, 18.2, 18.3, 18.4, 18.5, 18.6, 18.7, 18.8, 18.9, 19.0, 19.1, 19.2,19.3, 19.4, 19.5, 19.6, 19.7, 19.8, 19.9, 20.0, 20.1, 20.2, 20.3, 20.4,20.5, 20.6, 20.7, 20.8, 20.9, 21.0, 21.1, 21.2, 21.3, 21.4, 21.5, 21.6,21.7, 21.8, 21.9, 22.0, 22.1, 22.2, 22.3, 22.4, 22.5, 22.6, 22.7, 22.8,22.9, 23.0, 23.1, 23.2, 23.3, 23.4, 23.5, 23.6, 23.7, 23.8, 23.9, 24.0,24.1, 24.2, 24.3, 24.4, 24.5, 24.6, 24.7, 24.8, 24.9, 25.0, 25.1, 25.2,25.3, 25.4, 25.5, 25.6, 25.7, 25.8, 25.9, 26.0, 26.1, 26.2, 26.3, 26.4,26.5, 26.6, 26.7, 26.8, 26.9, 27.0, 27.1, 27.2, 27.3, 27.4, 27.5, 27.6,27.7, 27.8, 27.9, 28.0, 28.1, 28.2, 28.3, 28.4, 28.5, 28.6, 28.7, 28.8,28.9, 29.0, 29.1, 29.2, 29.3, 29.4, 29.5, 29.6, 29.7, 29.8, 29.9, 30,31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48,49, or 50 mm), including any and all ranges and subranges therein.

In some embodiments, the breathable structure and/or the fibroussubstrate has a density of 0.9 to 50 kg/m³ (e.g., 0.9, 1.0, 1.1, 1.2,1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6,2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0,4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4,5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8,6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2,8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6,9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8,10.9, 11.0, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0,12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2,13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, 14.0, 14.1, 14.2, 14.3, 14.4,14.5, 14.6, 14.7, 14.8, 14.9, 15.0, 15.1, 15.2, 15.3, 15.4, 15.5, 15.6,15.7, 15.8, 15.9, 16.0, 16.1, 16.2, 16.3, 16.4, 16.5, 16.6, 16.7, 16.8,16.9, 17.0, 17.1, 17.2, 17.3, 17.4, 17.5, 17.6, 17.7, 17.8, 17.9, 18.0,18.1, 18.2, 18.3, 18.4, 18.5, 18.6, 18.7, 18.8, 18.9, 19.0, 19.1, 19.2,19.3, 19.4, 19.5, 19.6, 19.7, 19.8, 19.9, 20.0, 20.1, 20.2, 20.3, 20.4,20.5, 20.6, 20.7, 20.8, 20.9, 21.0, 21.1, 21.2, 21.3, 21.4, 21.5, 21.6,21.7, 21.8, 21.9, 22.0, 22.1, 22.2, 22.3, 22.4, 22.5, 22.6, 22.7, 22.8,22.9, 23.0, 23.1, 23.2, 23.3, 23.4, 23.5, 23.6, 23.7, 23.8, 23.9, 24.0,24.1, 24.2, 24.3, 24.4, 24.5, 24.6, 24.7, 24.8, 24.9, 25.0, 25.1, 25.2,25.3, 25.4, 25.5, 25.6, 25.7, 25.8, 25.9, 26.0, 26.1, 26.2, 26.3, 26.4,26.5, 26.6, 26.7, 26.8, 26.9, 27.0, 27.1, 27.2, 27.3, 27.4, 27.5, 27.6,27.7, 27.8, 27.9, 28.0, 28.1, 28.2, 28.3, 28.4, 28.5, 28.6, 28.7, 28.8,28.9, 29.0, 29.1, 29.2, 29.3, 29.4, 29.5, 29.6, 29.7, 29.8, 29.9, 30,31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48,49, or 50 kg/m³), including any and all ranges and subranges therein.

In some embodiments, the breathable structure and/or the fibroussubstrate has a weight of 25 to 600 gsm (g/m²) (e.g., 25, 26, 27, 28,29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46,47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64,65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82,83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100,101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114,115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128,129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142,143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156,157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170,171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184,185, 186, 187, 188, 189, 190, 191, 192, 193, 194, 195, 196, 197, 198,199, 200, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 211, 212,213, 214, 215, 216, 217, 218, 219, 220, 221, 222, 223, 224, 225, 226,227, 228, 229, 230, 231, 232, 233, 234, 235, 236, 237, 238, 239, 240,241, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 253, 254,255, 256, 257, 258, 259, 260, 261, 262, 263, 264, 265, 266, 267, 268,269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282,283, 284, 285, 286, 287, 288, 289, 290, 291, 292, 293, 294, 295, 296,297, 298, 299, 300, 301, 302, 303, 304, 305, 306, 307, 308, 309, 310,311, 312, 313, 314, 315, 316, 317, 318, 319, 320, 321, 322, 323, 324,325, 326, 327, 328, 329, 330, 331, 332, 333, 334, 335, 336, 337, 338,339, 340, 341, 342, 343, 344, 345, 346, 347, 348, 349, 350, 351, 352,353, 354, 355, 356, 357, 358, 359, 360, 361, 362, 363, 364, 365, 366,367, 368, 369, 370, 371, 372, 373, 374, 375, 376, 377, 378, 379, 380,381, 382, 383, 384, 385, 386, 387, 388, 389, 390, 391, 392, 393, 394,395, 396, 397, 398, 399, 400, 401, 402, 403, 404, 405, 406, 407, 408,409, 410, 411, 412, 413, 414, 415, 416, 417, 418, 419, 420, 421, 422,423, 424, 425, 426, 427, 428, 429, 430, 431, 432, 433, 434, 435, 436,437, 438, 439, 440, 441, 442, 443, 444, 445, 446, 447, 448, 449, 450,451, 452, 453, 454, 455, 456, 457, 458, 459, 460, 461, 462, 463, 464,465, 466, 467, 468, 469, 470, 471, 472, 473, 474, 475, 476, 477, 478,479, 480, 481, 482, 483, 484, 485, 486, 487, 488, 489, 490, 491, 492,493, 494, 495, 496, 497, 498, 499, 500, 510, 520, 530, 540, 550, 560,570, 580, 590, or 600 gsm), including any and all ranges and subrangestherein.

In some embodiments, the breathable structure comprises a low densityhigh loft fibrous substrate (e.g., a high loft nonwoven) having, at aweight of 200 gsm, a thickness of at least about 20 mm (e.g., at least30 mm, or, e.g., about 28-48 mm), and a density of less than 10 kg/m³(e.g., less than about 7 kg/m³).

In some embodiments, the breathable structure comprises a high density(e.g., high density needled) fibrous substrate having, at a weight of200 gsm, a thickness of less than about 15 mm (e.g., less than 10 mm,or, e.g,. about 1-10 mm), and a density of greater than about 20 kg/m³(e.g., greater than about 30 kg/m³, e.g., about 35 to 45 kg/m³).

In some embodiments, the breathable structure and/or the fibroussubstrate has a drape of less than or equal to 3.5 cm, e.g., 1.0 cm to3.5 cm (e.g., 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0,2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, or3.5 cm), including any and all ranges and subranges therein, as measuredin accordance with Method ASTM D1388.

In some embodiments, the fibrous substrate of the breathable structurecomprises either one or more filaments of indefinite length, or aplurality of fibers.

In some embodiments, the plurality of fibers comprises staple fibers(i.e., fibers having a standardized length). For example, in someembodiments, the plurality of fibers comprises staple fibers having alength of 5 to 120 mm (e.g., 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34,35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52,53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70,71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88,89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104,105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118,119, or 120 mm), including any and all ranges and subranges therein(e.g., 12 to 90 mm, 40 to 60 mm, etc.).

Generally speaking, fibers may be crimped or uncrimped. Various crimps,including spiral and standard (e.g., planar) crimp, are known in theart.

While the fibers may be linear, optionally with crimp, in someembodiments, the fibrous substrate comprises fibers that have adesirable shape that is not linear or linear with crimp. While personshaving ordinary skill in the art are familiar with various desirableshapes to choose for the fiber, which are contemplated as being used inembodiments of the invention, some non-limiting examples includeY-shaped fibers, bow-tie shaped fibers, etc.

In some embodiments, the plurality of fibers is actually one or morefilaments. A filament is a single long threadlike continuous textilefiber/strand. Unlike staple fibers, which are of finite length,filaments are of indefinite length, and can run for yards or miles. Insome embodiments, the filament ranges in length from 5 inches to severalmiles, including any and all ranges and subranges therein. For example,in some embodiments, the filament may be at least 5 inches in length(e.g., at least 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37,38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55,56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73,74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91,92, 93, 94, 95, 96, 97, 98, 99, or 100 inches in length, or any range orsubrange therein). In some embodiments, the filaments may be at least 1foot in length (e.g., at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30,31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48,49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66,67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84,85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 110,120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250,260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390,400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530,540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670,680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810,820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950,960, 970, 980, 990, or 1000 feet in length, or any range or subrangetherein).

In some embodiments, the plurality of fibers in the fibrous substratecomprises synthetic fibers. Many synthetic fibers are known in the art,and any desired synthetic fibers may be used in the invention. Indeed,different fibers have different properties, and lend themselves towardadvantageous uses in different applications. This information is wellwithin the purview of persons having ordinary skill in the art. While awide array of synthetic fibers may be used in the invention, in someembodiments, nonexclusive synthetic fibers that may be used in theinvention are selected from nylon, polyester, polypropylene, polylacticacid (PLA), poly(butyl acrylate) (PBA), polyamide, acrylic, acrylate,acetate, polyolefin, nylon, rayon, lyocell, aramid, spandex, viscose,and modal fibers, and combinations thereof. In particular embodiments,synthetic fibers comprise polyester fibers. For example, in someembodiments, the polyester is selected from poly(ethyleneterephthalate), poly(hexahydro-p-xylylene terephthalate), poly(butyleneterephthalate), poly-1,4-cyclohexelyne dimethylene (PCDT),polytrimethylene terephthalate (PTT), and terephthalate copolyesters inwhich at least 85 mole percent of the ester units are ethyleneterephthalate or hexahydro-p-xylylene terephthalate units. In aparticular embodiment, the polyester is polyethylene terephthalate. Insome embodiments, the synthetic fibers comprise virgin fibers. In someembodiments, the synthetic fibers comprise recycled fibers (e.g.,recycled polyester fibers).

The plurality of fibers comprises 0 to 100 wt % synthetic fibers, forexample, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17,18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53,54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71,72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89,90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100 wt %, including any andall ranges and subranges therein (e.g., 10 to 100 wt %, 30 to 100 wt %,51 to 100 wt %, 40 to 90 wt %, 20 to 80 wt %, etc.). In someembodiments, the fiber mixture comprises greater than 50, 55, 60, 65,70, or 75 wt % synthetic fibers.

Denier is a unit of measure defined as the weight in grams of 9000meters of a fiber or yarn. It is a common way to specify the weight (orsize) of the fiber or yarn. For example, polyester fibers that are 1.0denier typically have a diameter of approximately 10 micrometers.Micro-denier fibers are those having a denier of 1.0 or less, whilemacro-denier fibers have a denier greater than 1.0.

In some embodiments, the synthetic fibers have a denier of 0.7 denier to8.0 denier, including any and all ranges and subranges therein. Forexample, in some embodiments, the synthetic fibers have a denier of 0.7,0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1,2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5,3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9,5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3,6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7,7.8, 7.9, or 8.0 denier, including any and all ranges and subrangestherein.

In some embodiments, the synthetic fibers comprise micro-denier fibers(e.g., fibers having a denier of 0.7 to 1.0 denier). In someembodiments, the synthetic fibers comprise macro-denier fibers (e.g.,fibers having a denier of 1.1 to 8.0 denier). In some embodiments, thesynthetic fibers comprise micro-denier fibers and macro-denier fibers.

In some embodiments, the plurality of fibers comprises synthetic fibersthat are siliconized.

The term “siliconized” means that the fiber is coated with asilicon-comprising composition (e.g., a silicone). Siliconizationtechniques are well known in the art, and are described, e.g., in U.S.Pat. No. 3,454,422. The silicon-comprising composition may be appliedusing any method known in the art, e.g., spraying, mixing, dipping,padding, etc. The silicon-comprising (e.g., silicone) composition, whichmay include an organosiloxane or polysiloxane, bonds to an exteriorportion of the fiber. In some embodiments, the silicone coating is apolysiloxane such as a methylhydrogenpolysiloxane, modifiedmethylhydrogenpolysiloxane, polydimethylsiloxane, or amino modifieddimethylpolysiloxane. As is known in the art, the silicon-comprisingcomposition may be applied directly to the fiber, or may be diluted witha solvent as a solution or emulsion, e.g. an aqueous emulsion of apolysiloxane, prior to application. Following treatment, the coating maybe dried and/or cured.

As is known in the art, a catalyst may be used to accelerate the curingof the silicon-comprising composition (e.g., polysiloxane containingSi—H bonds) and, for convenience, may be added to a silicon-comprisingcomposition emulsion, with the resultant combination being used to treatthe synthetic fiber. Suitable catalysts include iron, cobalt, manganese,lead, zinc, and tin salts of carboxylic acids such as acetates,octanoates, naphthenates and oleates. In some embodiments, followingsiliconization, the fiber may be dried to remove residual solvent andthen optionally heated to between 65° and 200° C. to cure.

Of the plurality of fibers, 0 to 100 wt % (e.g., 0, 1, 2, 3, 4, 5, 6, 7,8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25,26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43,44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61,62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79,80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97,98, 99, or 100 wt %, including any and all ranges and subranges therein)of the synthetic fibers, if present, are siliconized

In some embodiments, the plurality of fibers comprises natural fibers.For example, in some embodiments, the plurality of fibers comprises oneor more members selected from wool, cotton, tencel, kapok (cotton-likefluff obtained from seeds of a Kapok tree, which may optionally befurther processed before use), flax, animal hair, silk, and down (e.g.,duck or goose down).

The plurality of fibers comprises 0 to 100 wt % natural fibers, forexample, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17,18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53,54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71,72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89,90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100 wt %, including any andall ranges and subranges therein (e.g., 0 to 50 wt %, 1 to 40 wt %, 5 to25 wt %, 30 to 60 wt %, etc.). In some embodiments, the fiber mixturecomprises less than 50, 40, 30, 20, or 10 wt % natural fibers.

In some embodiments, the fiber mixture comprises only synthetic fibers.In some embodiments, the fiber mixture comprises only natural fibers. Insome embodiments, the fiber mixture comprises synthetic fibers andnatural fibers.

In some embodiments, the plurality of fibers comprises 0 to 25 wt %synthetic binder fibers, said binder fibers having a bonding temperaturelower than the softening temperature of synthetic fibers present in theplurality of fibers.

In some embodiments, the synthetic binder fibers make up, e.g., 0, 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,23, 24, or 25 wt % of the plurality of fibers, including any and allranges and subranges therein.

In some embodiments, the synthetic binder fibers have a denier of 1.0 to6.0 denier (e.g., 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0,2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4,3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8,4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, or 6.0 denier),including any and all ranges and subranges therein (e.g., 1.0 to 3.0denier, 1.5 to 2.5 denier, etc.).

In some embodiments, the binder fibers have a staple cut length of 38 to105 mm, including any and all ranges and subranges therein. For example,in some embodiments, the length is 38, 39, 40, 41, 42, 43, 44, 45, 46,47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64,65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82,83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100,101, 102, 103, 104, or 105 mm, including any and all ranges/subrangestherein (e.g., 38-51 mm).

As indicated above, the binder fibers have a bonding temperature lowerthan the softening temperature of any synthetic fibers present in theplurality of fibers. In some embodiments, the binder fibers have abonding temperature of less than or equal to 200° C. In someembodiments, the binder fibers have a bonding temperature of 50 to 200°C., including any and all ranges and subranges therein. In someembodiments, the binder fibers have a bonding temperature of 80° C. to150° C. In some embodiments, the binder fibers have a bondingtemperature of 100° C. to 125° C.

In some embodiments, the binder fibers comprise low-melt polyesterfibers.

In some embodiments, the binder fibers are bicomponent fibers comprisinga sheath and a core, wherein the sheath comprises a material having alower melting point than the core.

In some embodiments, the fibrous substrate comprises binder fibers, andhas been heat treated so as to melt all or a portion of the binderfibers. Persons having ordinary skill in the art will understand that,in such embodiments, although “binder fibers” may be recited in thefibrous substrate, said fibers may be wholly or partially melted fibers,as opposed to binder fibers in their original, pre-heat treatment form.

In some embodiments of the fibrous substrate, the fiber members of theplurality of fibers are homogenously mixed, meaning, the fiber mixtureof the plurality of fibers has a substantially uniform (i.e., 90 -100%uniform) composition.

The breathable structure comprises a cross-linked polymer that compriseshydrophobic moieties.

In some embodiments, the cross-linked polymer is fluorine-free.

In some embodiments, the cross-linked polymer does not comprise afluorocarbon.

In some embodiments, the cross-linked polymer comprises cationicmoieties.

In some embodiments, the cross-linked polymer comprises hydrocarbongroups (e.g., aliphatic hydrocarbon groups) that impart water repellencyon the polymer. In some embodiments, the cross-linked polymer compriseschemically reactive groups for bonding to fibrous substrate surfaces.

In some embodiments, the polymer is formed from a polymeric compositioncomprising one or more self-crosslinking water-dispersible polymers(including copolymers) that can crosslink by application of thermaland/or photoinitiated stimuli. Examples of non-limiting polymers includethe acrylic (co)polymers described in United States Patent ApplicationNo. 20170030010. In some embodiments, the self-crosslinkingwater-dispersible polymers comprise hydrocarbon groups (e.g., aliphatichydrocarbon groups). In some embodiments, the self-crosslinkingwater-dispersible polymers comprise chemically reactive groups forbonding to fibrous surfaces and/or for crosslinking the polymers uponbeing subjected to an external stimulus such as heat.

In some embodiments, the polymer is formed from a polymeric compositioncomprising one or more polymers and/or prepolymers (e.g., monomers)having a weight average molecular weight (Mw) of 1,000 to 2,500 Daltons(e.g., 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000,2100, 2200, 2300, 2400, or 2500 Da, including any and all ranges andsubranges therein, e.g., 1400 -2000 Da, 1500 -1800 Da, etc.), asmeasured using gel permeation chromatography (GPC) with polystyrenestandard.

In some embodiments, the polymer is formed from a polymeric compositioncomprising a hydrocarbon (e.g., a constituent having an alkyl chain(e.g., C₄-C₂₀ alkyl, such as C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃,C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, C₁₉, or C₂₀, or any range therein, e.g.,C₆-C₁₄, C₈-C₁₂, etc.), a hydrocarbon wax, etc.). In some embodiments,the composition comprises a constituent having an alkyl chain with aterminal CH₃.

In some embodiments, the polymer is formed from a polymeric compositioncomprising one or more melamine rings.

In some embodiments, the polymer is formed from a polymeric compositionthat comprises formaldehyde.

In some embodiments, the polymer is formed from a polymeric compositioncomprising a melamine formaldehyde resin.

In some embodiments, the polymer is formed from a polymer compositioncomprising a functionalized melamine prepolymer, e.g., an alkyl (e.g.,C₈-C₁₂ alkyl) functionalized melamine compound.

In some embodiments, the polymer formed from a polymeric compositioncomprises less than 1 wt % formaldehyde (e.g., less than 0.90, 0.91,0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, or 0.99 wt %).

In some embodiments, the polymer is formed from a relativelymonodisperse polymeric composition. In some embodiments, the polymericcomposition has a dispersity (Mw/Mn) from GPC of 0.90 to 1.50. Forexample, in some embodiments, the PDI is 0.90, 0.91, 0.92, 0.93, 0.94,0.95, 0.96, 0.97, 0.98, 0.99, 1.0, 1.01, 1.02, 1.03, 1.04, 1.05, 1.06,1.07, 1.08, 1.09, 1.10, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18,1.19, 1.20, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.30,1.31, 1.32, 1.33, 1.34, 1.35, 1.36, 1.37, 1.38, 1.39, 1.40, 1.41, 1.42,1.43, 1.44, 1.45, 1.46, 1.47, 1.48, 1.49, or 1.50, including any and allranges and subranges therein (e.g., 1.0 to 1.45, 1.1 to 1.35, etc.).

In some embodiments, the polymer formed from a polymeric compositiondoes not comprise any free (non-polymerized) formaldehyde.

In some embodiments, the polymer is formed from a polymeric compositionthat comprises Altopel F³ (a commercially-available, fluorine-freehydrophobe-fortified self-crosslinking polymer marketed as a waterrepellent by Bolger & O'Hearn, Inc.)

In some embodiments, the polymeric composition is comprised within apolymer solution (e.g., a solvent-based solution, such as anaqueous-based solution) that comprises one or more additionalcomponents, such as an emulsifier or surfactant. Various additionalcomponents are described, e.g., in United States Application No.20120114928. Emulsifiers and surfactants are well known in the art. Insome embodiments, the solution comprises a cationic and/or non-ionicemulsifier or surfactant.

In various embodiments, the polymer solution is applied to the fibroussubstrate (for example, by spraying the polymer solution onto thefibrous substrate, dipping the fibrous substrate in the polymersolution, or kiss-rolling the polymer solution onto the fibroussubstrate), thereby coating portions of the plurality of fibers in thefibrous substrate with the polymer solution. The solution-appliedfibrous substrate can then be subjected to a stimulus (e.g., heat) thatcross-links the polymer, thereby forming the cross-linked polymer, whichcoats portions of the plurality of fibers.

FIG. 1 depicts a portion of a fibrous substrate, nonwoven web 10, whichcomprises polyester fibers 12. FIG. 2 is an enlarged view of nonwovenweb 10, and depicts the polyester fibers 12 and binder fibers 16 which,in FIG. 2, have melted following heat treatment of the web, thus bondingtogether fibers within the web 10. In FIG. 2, there are various pointsof overlap 14, wherein fibers 12 overlap with one another and/or withbinder fibers 16. Depending on the proximity of fibers (due to, e.g.,number of fibers, density of substrate, etc.) some fibrous substrateembodiments will have more points of overlap 14 than others. As would bereadily understood by persons having ordinary skill in the art, where afibrous substrate has more points of overlap 14, there will often beless fiber surface area available to be coated by the polymer.

In some embodiments of the inventive breathable structure, 40 to 100%(e.g., 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55,56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73,74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91,92, 93, 94, 95, 96, 97, 98, 99, 99.5, or 100%) of the surface area ofthe fibers in the fibrous substrate, including any and all ranges andsubranges therein (e.g., 40-100%, 50 to 99%, 60 to 98%, 70 to 97%, 80 to96%, 90 to 100%, etc.) is in direct contact with the cross-linkedpolymer. Where fibers have been treated with other chemistries, e.g.,siliconization, the surface area of the chemistry-treated fibers willstill be considered to be in direct contact with the cross-linkedpolymer, notwithstanding such chemistry (e.g., siliconization).

In some embodiments of the inventive breathable structure, greater thanor equal to 40% (e.g., greater than or equal to 40, 41, 42, 43, 44, 45,46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63,64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81,82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or99%) of the surface area of the fibers in the fibrous substrate is indirect contact with the cross-linked polymer.

In some embodiments, the inventive breathable structure comprises 0.25wt % to 7 wt % (e.g., 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1,1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5,2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9,4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3,5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7,6.8, 6.9, or 7.0 wt %) of the cross-linked polymer, including any andall ranges and subranges therein (e.g., 1 to 5 wt %).

The term hydrostatic resistance, which may be used interchangeablyherein with the term hydrostatic head, is a measure of the resistance ofa structure to penetration by liquid water under static pressure.Hydrostatic resistance/hydrostatic head, as used herein, is calculatedaccording to AATCC-127, which is hereby incorporated by referenceherein, and is reported in centimeters of water. In some embodiments,the inventive breathable structure has a hydrostatic resistance of 30 to700 cm of water (e.g., 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130,140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270,280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410,420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550,560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, or700 cm of water), including any and all ranges and subranges therein. Insome embodiments, the inventive breathable structure has a hydrostaticresistance of greater than or equal to 50 cm of water.

In some embodiments, the breathable structure has a hydrostaticresistance of HR2, and the fibrous substrate (or, breathable structure,in the absence of the cross-linked polymer), has a hydrostaticresistance of HR1, wherein:

${\frac{\left( {{HR2} - {HR1}} \right)}{HR1} \times 100\%} \geq {50\%\mspace{14mu}\left( {{e.g.},{\geq 50},51,} \right.}$

52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69,70, 71, 72, 73, 74, or 75%).

In some embodiments, the breathable structure has a moisture vaportransmission rate (MVTR) (calculated according to ASTM E-96B, which ishereby incorporated by reference herein), of 200 to 1500 g/m²/day (e.g.,200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330,340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470,480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610,620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750,760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890,900, 910, 920, 930, 940, 950, 960, 970, 980, 990, 1000, 1010, 1020,1030, 1040, 1050, 1060, 1070, 1080, 1090, 1100, 1110, 1120, 1130, 1140,1150, 1160, 1170, 1180, 1190, 1200, 1210, 1220, 1230, 1240, 1250, 1260,1270, 1280, 1290, 1300, 1310, 1320, 1330, 1340, 1350, 1360, 1370, 1380,1390, 1400, 1410, 1420, 1430, 1440, 1450, 1460, 1470, 1480, 1490, or1500 g/m²/day), including any and all ranges and subranges therein. Insome embodiments, the breathable structure has a MVTR of greater than orequal to 300 g/m²/day.

In some embodiments, the breathable structure has a Frazier AirPermeability (calculated according to ASTM D737, which is herebyincorporated by reference herein), of 1 to 500 cfm (e.g., 1, 2, 3, 4, 5,6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24,25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42,43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60,61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78,79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96,97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111,112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125,126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139,140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153,154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167,168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181,182, 183, 184, 185, 186, 187, 188, 189, 190, 191, 192, 193, 194, 195,196, 197, 198, 199, 200, 201, 202, 203, 204, 205, 206, 207, 208, 209,210, 211, 212, 213, 214, 215, 216, 217, 218, 219, 220, 221, 222, 223,224, 225, 226, 227, 228, 229, 230, 231, 232, 233, 234, 235, 236, 237,238, 239, 240, 241, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251,252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263, 264, 265,266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279,280, 281, 282, 283, 284, 285, 286, 287, 288, 289, 290, 291, 292, 293,294, 295, 296, 297, 298, 299, 300, 301, 302, 303, 304, 305, 306, 307,308, 309, 310, 311, 312, 313, 314, 315, 316, 317, 318, 319, 320, 321,322, 323, 324, 325, 326, 327, 328, 329, 330, 331, 332, 333, 334, 335,336, 337, 338, 339, 340, 341, 342, 343, 344, 345, 346, 347, 348, 349,350, 351, 352, 353, 354, 355, 356, 357, 358, 359, 360, 361, 362, 363,364, 365, 366, 367, 368, 369, 370, 371, 372, 373, 374, 375, 376, 377,378, 379, 380, 381, 382, 383, 384, 385, 386, 387, 388, 389, 390, 391,392, 393, 394, 395, 396, 397, 398, 399, 400, 401, 402, 403, 404, 405,406, 407, 408, 409, 410, 411, 412, 413, 414, 415, 416, 417, 418, 419,420, 421, 422, 423, 424, 425, 426, 427, 428, 429, 430, 431, 432, 433,434, 435, 436, 437, 438, 439, 440, 441, 442, 443, 444, 445, 446, 447,448, 449, 450, 451, 452, 453, 454, 455, 456, 457, 458, 459, 460, 461,462, 463, 464, 465, 466, 467, 468, 469, 470, 471, 472, 473, 474, 475,476, 477, 478, 479, 480, 481, 482, 483, 484, 485, 486, 487, 488, 489,490, 491, 492, 493, 494, 495, 496, 497, 498, 499, or 500 cfm), includingany and all ranges and subranges therein.

In some embodiments, the fibrous substrate is as listed in Table I:

TABLE 1 Fibrous Substrate Frazier Air Permeability Fabric 1 to 160 cfmHigh loft nonwoven 250 500 cfm

In some embodiments, the inventive breathable structure has a moisturevapor transmission rate of MVTR2, and the breathable structure, in theabsence of the cross-linked polymer (i.e., the uncoated fibroussubstrate), has a moisture vapor transmission rate of MVTR1, and:

${\frac{\left( {{MVTR1} - {MVTR2}} \right)}{MVTR1} \times 100\%} \leq {10{\%.}}$

For example, in some embodiments,

${{\frac{\left( {{{MVTR}\; 1} - {{MVTR}\; 2}} \right)}{{MVTR}\; 1} \times 100\%} \leq 10},9,8,7,6,5,4,3,{{or}\mspace{14mu} 2{\%.}}$

In some embodiments, the inventive breathable structure has a Frazierair permeability of AP2, and the breathable structure, in the absence ofthe cross-linked polymer (i.e., the uncoated fibrous substrate), has aFrazier air permeability of AP1, and:

${\frac{\left( {{AP1} - {AP2}} \right)}{AP1} \times 100\%} \leq {10{\%.}}$

For example, in some embodiments,

${{\frac{\left( {{AP1} - {AP2}} \right)}{AP1} \times 100\%} \leq 10},9,8,7,6,5,4,3,{{or}\mspace{14mu} 2{\%.}}$

In a second aspect, the invention provides an article comprising thebreathable structure according to the first aspect of the invention.

Non-limiting examples of inventive articles include, for example,garments (e.g. outerwear garments such as coats, jackets, other raingear, etc.), clothing, pillows, pads, sleeping bags, bedding (e.g.,quilts, comforters), etc.

In some embodiments, the article is fabric or insulation (e.g., batting,fleece, flannel, etc.). In some embodiments, the article is a productcomprising fabric or insulation (e.g., a sleeping bag, outerwear, activewear, a home good, etc.).

In a third aspect, the invention provides a method of making thebreathable structure according to the first aspect of the invention, orthe article according to the second aspect of the invention.

In some embodiments, the inventive method comprises applying to afibrous substrate a polymer solution comprising a cross-linkable polymercomprising hydrophobic moieties, thereby forming an intermediatestructure, then heating the intermediate structure, therebycross-linking the polymer.

While the polymer solution may be applied in any art acceptable manner,in some embodiments, applying the polymer solution to the fibroussubstrate comprises spraying the polymer solution onto the fibroussubstrate, dipping the fibrous substrate in the polymer solution, orkiss-rolling the polymer solution onto the fibrous substrate.

In some embodiments, the polymer solution comprises 0.5 to 10 wt % ofthe cross-linkable polymer (e.g., 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1,1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5,2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9,4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3,5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7,6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1,8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5,9.6, 9.7, 9.8, 9.9, or 10.0 wt %), including any and all ranges andsubranges therein (e.g., 1 to 5 wt %).

In some embodiments, the invention is as described in the followingclauses:

1. A breathable structure comprising a fibrous substrate and across-linked polymer comprising hydrophobic moieties, wherein thefibrous substrate comprises a plurality of fibers, and wherein thecross-linked polymer coats portions of the plurality of fibers.

2. The breathable structure according to clause 1, wherein the pluralityof fibers comprise synthetic fibers.

3. The breathable structure according to clause 1 or clause 2, whereinthe plurality of fibers comprise natural fibers.

4. The breathable structure according to any one of the precedingclauses, wherein greater than or equal to 50 wt % of the fibers in thefibrous substrate are synthetic fibers.

5. The breathable structure according to any one of the precedingclauses, wherein greater than or equal to 40% of the surface area of thefibers in the fibrous substrate is in direct contact with thecross-linked polymer.

6. The breathable structure according to clause 5, wherein greater thanor equal to 60% of the surface area of the fibers in the fibroussubstrate is in direct contact with the cross-linked polymer.

7. The breathable structure according to any one of the precedingclauses, comprising 0.25 wt % to 7 wt % of the cross-linked polymer.

8. The breathable structure according to clause 7, comprising 1 wt % to5 wt % of the cross-linked polymer.

9. The breathable structure according to any one of the precedingclauses, wherein the cross-linked polymer does not comprise fluorine.

10. The breathable structure according to any one of the precedingclauses, wherein the structure does not comprise a fluorocarbon.

11. The breathable structure according to any one of the precedingclauses, wherein the plurality of fibers comprises polyester fibers.

12. The breathable structure according to any one of the precedingclauses, wherein the fibrous substrate is a non-woven web.

13. The breathable structure according to any one of clauses 1-11,wherein the fibrous substrate is fleece.

14. The breathable structure according to any one of clauses 1-11,wherein the fibrous substrate is fabric.

15. The breathable structure according to any one of clauses 1-11,wherein the fibrous substrate is non-woven insulation (e.g., high-loftnonwoven insulation, low-loft nonwoven insulation, or needled non-woveninsulation, such as high density needled non-woven insulation).

16. The breathable structure according to any one of the precedingclauses, having a hydrostatic resistance of greater than or equal to 50centimeters of water.

17. The breathable structure according to any one of the precedingclauses, having a hydrostatic resistance of HR2, wherein the breathablestructure, in the absence of the cross-linked polymer, has a hydrostaticresistance of HR1, and wherein:

${\frac{\left( {{HR2} - {HR1}} \right)}{HR1} \times 100\%} \geq {50{\%.}}$

18. The breathable structure according to any one of the precedingclauses, having a moisture vapor transmission rate (MVTR) of greaterthan or equal to 300 g/m²/day.

19. The breathable structure according to any one of the precedingclauses, having a Frazier air permeability of 1 to 500 cfm.

20. The breathable structure according to clause 19, having a Frazierair permeability of 1 to 160 cfm (e.g., 1 to 20 cfm), wherein thefibrous substrate is fabric.

21. The breathable structure according to clause 19, having a Frazierair permeability of 250 to 500 cfm, wherein the fibrous substrate is ahigh loft nonwoven.

22. The breathable structure according to any one of the precedingclauses, having a moisture vapor transmission rate of MVTR2 and aFrazier air permeability of AP2, wherein the breathable structure, inthe absence of the cross-linked polymer, has a moisture vaportransmission rate of MVTR1 and a Frazier air permeability of AP1, andwherein:

${{\frac{\left( {{MVTR1} - {MVTR2}} \right)}{MVTR1} \times 100\%} \leq {10\%}};\;{{and}/{or}}$${\frac{\left( {{AP1} - {AP2}} \right)}{AP1} \times 100\%} \leq {10{\%.}}$

23. An article comprising the breathable structure according to any oneof the preceding clauses.

24. The article according to clause 23, wherein said article is agarment.

25. A method of making the breathable structure according to any one ofclauses 1 to 22, the method comprising applying to a fibrous substrate apolymer solution comprising a cross-linkable polymer comprisinghydrophobic moieties, thereby forming an intermediate structure, thenheating the intermediate structure, thereby cross-linking the polymer.

26. The method according to clause 25, wherein said applying comprisesspraying the polymer solution onto the fibrous substrate, dipping thefibrous substrate in the polymer solution, or kiss-rolling the polymersolution onto the fibrous substrate.

27. The method according to clause 25 or clause 26, wherein the polymersolution comprises 0.5 to 10 wt % of the cross-linkable polymer.

28. The method according to clause 27, wherein the polymer solutioncomprises 1 to 5 wt % of the cross-linkable polymer.

EXAMPLE

The invention will now be illustrated, but not limited, by reference tothe specific embodiment described in the following example.

Example 1: An aqueous polymer solution is prepared by mixing Altopel F³(a commercially-available, fluorine-free hydrophobe-fortifiedself-crosslinking polymer marketed as a water repellent by Bolger &O'Hearn, Inc.) with water. The polymer solution is applied, viakiss-roll, to PET fleece. Polymers in the Altopel F³ are cross-linked byheat treating the coated fleece at about 175° C., resulting in abreathable structure comprising about 2 wt % of the cross-linkedpolymer. The result is a treated structure having good hydrostaticresistance, while maintaining surprisingly good breathability and airpermeability.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting of the invention. Asused herein, the singular forms “a”, “an” and “the” are intended toinclude the plural forms as well, unless the context clearly indicatesotherwise. It will be further understood that the terms “comprise” (andany form of comprise, such as “comprises” and “comprising”), “have” (andany form of have, such as “has” and “having”), “include” (and any formof include, such as “includes” and “including”), “contain” (and any formcontain, such as “contains” and “containing”), and any other grammaticalvariant thereof, are open-ended linking verbs. As a result, a method orarticle that “comprises”, “has”, “includes” or “contains” one or moresteps or elements possesses those one or more steps or elements, but isnot limited to possessing only those one or more steps or elements.Likewise, a step of a method or an element of an article that“comprises”, “has”, “includes” or “contains” one or more featurespossesses those one or more features, but is not limited to possessingonly those one or more features.

As used herein, the terms “comprising,” “has,” “including,”“containing,” and other grammatical variants thereof encompass the terms“consisting of” and “consisting essentially of.”

The phrase “consisting essentially of” or grammatical variants thereofwhen used herein are to be taken as specifying the stated features,integers, steps or components but do not preclude the addition of one ormore additional features, integers, steps, components or groups thereofbut only if the additional features, integers, steps, components orgroups thereof do not materially alter the basic and novelcharacteristics of the claimed compositions or methods.

All publications cited in this specification are herein incorporated byreference as if each individual publication were specifically andindividually indicated to be incorporated by reference herein as thoughfully set forth.

Subject matter incorporated by reference is not considered to be analternative to any claim limitations, unless otherwise explicitlyindicated.

Where one or more ranges are referred to throughout this specification,each range is intended to be a shorthand format for presentinginformation, where the range is understood to encompass each discretepoint within the range as if the same were fully set forth herein.

While several aspects and embodiments of the present invention have beendescribed and depicted herein, alternative aspects and embodiments maybe affected by those skilled in the art to accomplish the sameobjectives. Accordingly, this disclosure and the appended claims areintended to cover all such further and alternative aspects andembodiments as fall within the true spirit and scope of the invention.

1. A breathable structure comprising a fibrous substrate and across-linked polymer comprising hydrophobic moieties, wherein thefibrous substrate comprises a plurality of fibers, and wherein thecross-linked polymer coats portions of the plurality of fibers.
 2. Thebreathable structure according to claim 1, wherein the plurality offibers comprise synthetic fibers.
 3. The breathable structure accordingto claim 1, wherein the plurality of fibers comprise natural fibers. 4.The breathable structure according to claim 1, wherein greater than orequal to 50 wt % of the fibers in the fibrous substrate are syntheticfibers.
 5. The breathable structure according to claim 1, whereingreater than or equal to 40% of the surface area of the fibers in thefibrous substrate is in direct contact with the cross-linked polymer. 6.The breathable structure according to claim 5, wherein greater than orequal to 60% of the surface area of the fibers in the fibrous substrateis in direct contact with the cross-linked polymer.
 7. The breathablestructure according to claim 1, comprising 0.25 wt % to 7 wt % of thecross-linked polymer.
 8. The breathable structure according to claim 7,comprising 1 wt % to 5 wt % of the cross-linked polymer.
 9. Thebreathable structure according to claim 1, wherein the cross-linkedpolymer does not comprise fluorine.
 10. (canceled)
 11. The breathablestructure according to claim 1, wherein the plurality of fiberscomprises polyester fibers.
 12. The breathable structure according toclaim 1, wherein the fibrous substrate is a non-woven web. 13-15.(canceled)
 16. The breathable structure according to claim 1, having ahydrostatic resistance of greater than or equal to 50 centimeters ofwater.
 17. The breathable structure according to claim 1, having ahydrostatic resistance of HR2, wherein the breathable structure, in theabsence of the cross-linked polymer, has a hydrostatic resistance ofHR1, and wherein:(HR2−HR1)/HR1×100%≥50%.
 18. The breathable structure according to claim1, having a moisture vapor transmission rate (MVTR) of greater than orequal to 300 g/m²/day.
 19. The breathable structure according to claim1, having a Frazier air permeability of 1 to 500 cfm.
 20. The breathablestructure according to claim 19, wherein: the fibrous substrate isfabric having a Frazier air permeability of 1 to 160 cfm; or the fibroussubstrate is a high loft nonwoven having a Frazier air permeability of250 to 500 cfm.
 21. (canceled)
 22. The breathable structure according toclaim 1, having a moisture vapor transmission rate of MVTR2 and aFrazier air permeability of AP2, wherein the breathable structure, inthe absence of the cross-linked polymer, has a moisture vaportransmission rate of MVTR1 and a Frazier air permeability of AP1, andwherein:(MVTR1−MVTR2)/MVTR1×100%≤10%; and/or(AP1−AP2)/AP1×100%≤10%.
 23. An article comprising the breathablestructure according to claim
 1. 24. The article according to claim 23,wherein said article is a garment.
 25. A method of making the breathablestructure according to claim 1, the method comprising applying to afibrous substrate a polymer solution comprising a cross-linkable polymercomprising hydrophobic moieties, thereby forming an intermediatestructure, then heating the intermediate structure, therebycross-linking the polymer. 26-28. (canceled)